Process and apparatus for the conversion of hydrocarbon liquids and glases



l M. P. YOUKER PROCESS AND APPARATUS FOR THECONVERSION OF HYDROCARBON LIQUIDS AND GASES Filed DEC. 4, 1931 Dec. 7, 1937.

Canuerfcl,

of Gamba Y ra/ventola @R5/Ser Patented Dee. 7, 1937 PATENT OFFICE PROCESS AND APPARATUS FOR THE CON- VERSION OF HYDROCARBON LIQUIDS AND GASES Malcolm P. Youker, nartlesville, Okla., assignmto Phillips Petroleum Company, Bartlesville, Okla., a corporation of Delaware Application December 4, 1931, Serial No. 579,044

s claims.

This present invention is an improvement in processes which were originally disclosed in applications for patent filed in the United States Patent Office by Malcolm P. Youker under the following U. S. patent. serial numbers and filing dates: 27,234, May l, 1925, now U. S. Patent 1,800,586; 534,067, April 30, 1931; 545,309, June 18, 1931, now U. S. Patent 2,035,036.

In converting hydrocarbon gases to hydrocarbon liquids by means of heating such gases in the presence of fuel oil or gas oil, as disclosed in said patent applications, I have found that the apparatus has a tendency to coke up rather rapidly. In this application for patent I will disclose a particular method and apparatus by which a mixture of hydrocarbon gases and heavy hydrocarbon oil or any hydrocarbon material may be continuously heated and converted while at the same time a minimum amount of carbon will be deposited in the apparatus. An object of my invention is to provide a process and apparatus by which either vgaseous or liquid hydrocarbon materials may be converted to new hydrocarbon f compounds Without the production of excessive quantities of free carbon. This object and other objects which will be made apparent in the following specilcation are accomplished by my new process and apparatus.

My new process will be understood from the following specification taken in connection with the attached drawing on which a form of apparatus by which my new process may be carried out is illustrated.

Referring to the drawing, the numeral I designates a furnace in the bottom of which is mounted a gas burner 2. Any suitable means of iiring the bottom of this furnace may be-utilized, the gas burner being shown hereon for purposes of illustration. The numeral 3 designates a conversion chamber.'l The numeral 4 designates a. smoke stack. A breeching 5 leads from the top of the furnace I into the smoke stack 4. A breeching 6 leads from breaching 5 into the top of chamber 3. A damper 1 is mounted in breaching 5 at a point between smoke stack 4 and breeching 6 and may be operated to restrict the ilow of gases through breeching 5 into smoke stack 4. A breeching 8 leads from the bottom of chamber 3 into the smoke stack 4. A damper 9 is mounted in stack 4 and may be operated to control the flow of' gases through chamber 3 into smoke stack 4. Fuel may be fired in the bottom of furnace I and the gases of combustion resulting therefrom will flow upward through this furnace and thence from the top of furnace I through breeching 5 (ol. 19e-51) into vsmoke stack 4. By partially closing damper 1 and partially opening damper 9 a portion of the gases of combustion which ow through breeching .5 may be diverted therefrom and caused to flow through breeching '6 and downward through chamber '3 and through breechng 8 into smoke stack 4. It is apparent that by manipulation of dampers 'l and 9 any desired percentage of the stack gases leaving 'furnace I `may be causedv to flow downward through the conversion chamber 3. A breeching I5 interconnects breaching 6 with stack 4. A fan I6 is so mounted in-the breeching I5 as to propel gases from the stack 4 into the breeching 0. A tube I0 in which is mounted a pump II has a heating portion I0a which leads through furnace I lin several upward passes and also has a conversion portion I0b which leads through the conversion chamber 3 in several upward passes.l A valve I2 is mounted in that portion of the tube l'which projects beyond the chamber 3. mounted a pump I4 leads into the tube I0. Hydrocarbon liquid may be delivered through the tube I0 by means of the pump II. Normally gaseous hydrocarbons in either liquid or gaseous state may be delivered through the tube 'I0 by means of the pump I4 andthe pipe I3. The furnace I Will be red and hydrocarbon materials will be forced by pumps II or I4 through the tube I0. Pressure will be maintained in the tube I0 by means of manipulating the valve I2. The burner 2 will be so regulated that hydrocarbon materials passing by way of tube I0 through furnace I will be heated therein to the proper temperature for conversion, which in most cases will range between 800 degrees F. and 1,000 degrees F. The heated material after leaving furnace I will pass through that part of the tube I0 which is disposed in the chamber 3 and by manipulation of the dampers I and 9 a portion of the gases of combustion which leave the furnace I will pass through the chamber 3y and serve to prevent loss of heat from that part of the tube I0 which is mounted in said chamber 3. In some cases a sufcient quantity of gases of combustion will be caused to flow through chamber 3 to heat the tube I0 to a limited degree. The fan I6 will be operated to recirculate through the chamber 3 gases which have already passed through chamber 3. The recirculated gas will be cooler than the gases of combustion which are delivered from breeching 5 through breeching 6 toward the chamber 3 and such recirculation of gases will result in the obtainance of a milder heating of the conversion tube in the chamber 3. By the A pipe I3 in which is y above described recirculation of gases of combustion the gases of combustion which pass from the breeching 5 through the breeching 6 and the chamber 3 are cooled before entering the chamber 3. This cooling of the gases of combustion which pass from the breeching 5 through the breeching 6 and the chamber 3 may be obtained by feeding cold air or any other cooling medium through the fan I6 into the `breeching 6, and I may elect to use some cooling medium such as air in this manner. The pressure maintained in the tube III will be varied to suit the particular material which is being converted. For some ma-4 terials it may be found desirable to maintain a pressure in the tubel I0 as low as 300 pounds per square inch while in other cases it may be desirable to maintain a pressure in the tube Illas high as 3,500 pounds per square inch.

In order to heat and convert hydrocarbon. materials while passing through a tube, it is necessary that these materials pass through a considerable length of. tube after they have been heated to la conversion temperature. It hasxbeen customary inthe past vto mount in a.furnace a heating tube which is sufficiently long to. provide time for conversion after conversion temperaturehas been obtained lin the tube, and this arrangement has been to some extent satlisfac-"I4 tory; however, I have found that due to the fact that all of the gases of combustion pass over the entire tube such an arrangement is apt to cause theformation of free carbon in excessive quantities in the conversion portion of the tube and the deposition of this carbon necessitates the frequentshutting down of such equipment for cleaning purposes. I find that it is much more desirable to divide this tube into a heating portion and a conversion portion, the former portion being subjected to rapid heating while the latter portion is subjected to only very gentle heating, if any. That partof the tube III or heating portion which is mounted in the furnace I is used` for rapidly bringing the hydrocarbon material to conversion temperature while that'part .of the tube III or conversion portion which ismounted g in chamber 3 is` provided for the purpose of retaining the materials to be converted at conversion temperature through a 'suflicient period of time to permit the conversion reaction to proceed to somewhere near equilibrium. The hydrocarbon material having been brought to conversion temperature in the furnace I, conversion of the same may be obtained in chamber 3, even though no heating is accomplished in chamber 3, provided that' this chamber is well insulated. to preventheat loss from that part of the tube I 0 which is mounted therein. The provision which I have shown for passing stack gases through the chamber 3 is a method by which heat loss to surrounding objects from the conversion portion of the tube III may be prevented and by which gentle heating of the materials undergoing conversion may be accomplished, thus supplying heat for an endothermic reaction.

After' the converted hydrocarbon materials pass `the valve I2 they will of course be largely in a vapor phase and any of the conventional sys-'- tems of fractionating columns and condensers may be utilized to separate these converted materials into various fractions and condense and cool them.

Numerous other arrangements of a similar nature could be made. While I have described in detail one arrangement of a combined heating and conversion tube, I do not wish to limit myself in my claims to this particular arrangement but Wish to claim broadly al1 of the advantages which are inherent in my new process,the fundamental principle of which is that hydrocarbon materials which' are to be converted are rst heated in a heating portion of a tube through which such materials are caused to ow progressively and, second, these materials are caused to flow through a conversion portion of said tube in whichconversion of such materials is accomplished, the second stage being accomplished under heating conditions which are at least more gentle than those conditions which are now conventionally utilized 4for this purpose. It is obvious that the heating of the chamber 3 may be accomplished by directly ring this chamber and that the method of heating this chamber which I have outlined is an economy measure. `While that part of the tube I0 which is mounted in the chamber 3 may be of larger cross-sectional area than that part of the tube I0 which is mounted in the furnace I, the cross-sectional area of any part of the tube I0 will be so restricted with respect to the quantity of materials which will be caused to flow through tube I0 thatv no part of the material caused to flow through tube I0 will lag materially behind the main body of materials flowing therethrough.

- It is desirable that the length of that.portion of thetube I0 which is mounted in the chamber 3 shall be equal to or greater than the lengthI of that portion of the tube I 0 which is mounted in the furnace I. For ordinary practical use, about 2,000 linear feet of 21/2" inside diameter tubingA may be mounted in the furnace I and about 3,000

' linear feet of 21/2 inside diameter, or 3" inside diameter, tubing may be mounted in the chamber 3. Such an arrangement of tubing will be found to give excellent results. In any particular case l it will be found desirable to carry out certain experiments to determine the relative length of tubing requiredA for heating and converting. In general, higher pressures maintained in the tube I0 will reduce the necessary length of tubing used for conversion purposes and vice versa.

I claim: i

1. A process for the conversion of hydrocarbon fluids, comprising passing a hydrocarbon fluid through a portion of a tube in a heating chamber, generating hot gases of combustion and passing the same in contact with said portion of the tube to heat the fluid to conversion temperatures, subsequently passing the heated fluid while at conversion temperatures into and through a conversion portion of said tube in a conversion chamber, discharging a portion of the gases of combustion from Vthe heating chamber while diverting another portion of said gases of combustion, after discharge from the heating chamber, into and through the conversion chamber,and introducing cooler diluent gases into the gases of combustion entering the conversion chamber for maintain- `ing the uid in the conversion portion of the tube at but notv above conversion temperatures, said diluent gases being recycled gases derived from gases discharged from the conversion chamber.

2. A process for the conversion of `iydrocarbon fluids comprising passing a. hydrocarbon fluid through a portion of a tube in a heating chamber, generating hot gases of combustion and passing vthe same in contact with said portion of the tube to heat the uid to conversion temperatures, subsequently passing the heated fluid while at conversion temperatures into and'through a conversion portion of said tube in a conversion chamber, discharging a portion of the gases of combustion from the heating chamber while diverting another portion of said gases of comfbustion, after discharge from the heating cham,-

ber, into and through the conversion chamber,

and introducing cooler diluent gases into the gases of combustion entering the conversion chamber for maintaining the iluid in the conversion portion of the tube at but not above conversion temperatures, said diluent gases being derived from gases discharged from the conversion chamber and being forced into the diverted combustion gases entering the conversion chamber.

3. A process for the conversion of hydrocarbon fluids, comprising passing a hydrocarbon uid lthrough a portion of a tube in a heating chamber, generating gases of combustion in said chamber and contacting said gases with said portion of the tube for heating the iluid to conversion tem-- peratures, passing the fluid from said portion of the tube while so heated through a conversion portion of the tube arranged in va. conversion.

chamber, discharging the gases of combustion from the heating chamber and dividing the discharged gases into iirst and second streams, discharging the iirst stream from the process, passing the second stream through the conversion chamber, and recirculating without reheating a portion of the second stream from the heating gas outlet of the conversion chamber back into the second stream as the latter enters the conversion chamber.,

A process for the conversion of hydrocarbon fluids, comprising iiowing a hydrocarbon fluid through a portion of a tube arranged in a heat-.-

ing chamber and heating said iluid in said portien to conversion temperatures, subsequently passing the heated iiuid through avconversion portion of said tube arranged in a conversion chamber while maintaining said uuid at but not above said conversion temperatures, generating hot eases of combustion and contacting said gases with the first mentioned portion of the tube for heating the iluid inthe ilrst portion ci ,the tube to said conversion temperatures, passing a portion of said hot gases of combustion through the conversion chamber, and diluting the last mentioned gases with cooler diluent gases for maintaining the iiuid in the conversion tube at but the latter. a. conduit portion of the tube connecty not above said con-version temperatures, said diiuting gases being a portion of the combustion gases discharged from the conversion chamber.

5. An apparatus for converting hydrocarbon iiuids, comprising'a heating chamber and a conversion chamber having an inlet and an outlet, a heating portion of a tube in the heating chamber, a conversion portion of the tube in the conversion chamber between the inlet and outlet of ing the outlet end ofjthe heating portion to the inlet. end of the conversion portion of the tube, a burner for generating gases of combustion for and third breechings, and for also causing some of the diverted gases of combustion to be recirculated from the conversion chamber through the fourth breeching into the second breeching. A

6. An apparatus for converting hydrocarbon uids, comprising a heating chamber and a conversion chamber, a heating portion of a tube in the heating chamber, a conversion portion of said tube in the conversion chamber, a conduit portion of the tube connecting the outlet end of the heating portion of the tube to the inlet end of Vthe conversion portion of the tube, a burner for generating gases of combustion for the heating chamber, a stack, a first breeching connecting the heating chamber to the stack for passing gases of combustion from that chamber to the stack, a second breeching connecting the first breeching to the inlet of the conversion chamber, a third breeching connecting the outlet of the conversion chamber to the stack, a fourth breeching connecting the stack to the second breeching at a point between the rst breeching and the inlet oi.' the conversion chamber, means in the rst breeching and Astack for causing some ofthe gases of combustion from the rst breeching to travel through the second and third breechings and for also allowing some of the diverted gases of combustion to be recirculated from the combustion chamber through the fourth breeching into the second breeching, and a fan in the fourth breeching for forcing stack gases into the second breeching, said means in thestack cooperating with the fan to recirculate combustion gases through the conversion chamber.

7. An apparatus for converting hydrocarbon uids, comprising a heating chamber and a conversion chamber, a heating portion of a tube in the heating chamber, a conversion portion of said tube in the conversion chamber, a conduit portion of said tube connecting the outlet end of the heating portion to the inlet end of the conversion portion, a burner for generating gases of combustion for the heating' chamber, a stack, a rst breeching connecting the heating chamber to the stack for passing gases of combustion from that chamber to the stack, a second breeching connecting the rst breeching to the inlet of the conversion chamber, a third breeching connecting the outlet of the conversion chamber to the stack,

' a fourth breeching connecting the stack to the second breeching at a point between the rst breeching and the inlet of the conversion chamber, means in the iirst breeching and stack for I allowing some of the gases of combustion from the ilrst breeching to travel from the conversion chamber through the second and third breechingsY and for allowing some of the diverted gases of combustion to be recirculated through the fourthcarbon-liquid and hydrocarbon gas into 'the inlet of the tube. l

8. An apparatus for converting hydrocarbon version chamber, a heating portion of -a tube in the heating chamber, a conversion portion of the tube in the conversion chamber, a conduit portion of said tube connecting the outlet end of the heating portion to the inlet end ofthe conversionv v portion, a burner for generating gases of combustion for the heating chamber, a stack, a flrst breeching connecting the beating chamber to the Y iluids, comprising a heating chamber and a constack for passing gases of combustion from that chamber to the stack, a second breechlng oonnecting the rst breeching to the inlet of the con- Jerslon chamber, a third breeching connecting the outlet of the conversion chamber to the stack, a fourth breeching connecting the stack to the second breechlng at a point between the first breeching and the conversion chamber, and

meansin the first breeching and stack for allow- A ing some of the gases of combustion from the first breeching to travel from the outlet of the conversion chamber through the second and third breechlngs and for allowing some of the diverted and approximately two and one-half inches inside ln diameterf MALCOLM P. YOUKER. 

